CN110791245A - Radiation curing adhesive composition, pressure-sensitive adhesive and protective film adhesive tape - Google Patents
Radiation curing adhesive composition, pressure-sensitive adhesive and protective film adhesive tape Download PDFInfo
- Publication number
- CN110791245A CN110791245A CN201911012463.9A CN201911012463A CN110791245A CN 110791245 A CN110791245 A CN 110791245A CN 201911012463 A CN201911012463 A CN 201911012463A CN 110791245 A CN110791245 A CN 110791245A
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- CN
- China
- Prior art keywords
- adhesive composition
- radiation
- pressure
- adhesive
- radiation curable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 81
- 230000001681 protective effect Effects 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 56
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 31
- 238000003847 radiation curing Methods 0.000 title abstract description 14
- 230000005855 radiation Effects 0.000 claims abstract description 45
- 239000010410 layer Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 13
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- 238000000576 coating method Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 7
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
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- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2471/00—Presence of polyether
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention discloses a radiation-curable adhesive, a pressure-sensitive adhesive and a protective film adhesive tape. The concentration of the oligomer is 25-99 wt% based on the total mass of the radiation curing adhesive composition, the molecular chain of the oligomer in the radiation curing adhesive composition has a polypropylene oxide structure, and the mass percentage of the polypropylene oxide structure in the adhesive composition is 20-95 wt%. The pressure-sensitive adhesive is obtained by directly crosslinking a radiation-curable adhesive composition through radiation. The invention also relates to a protective film adhesive tape prepared based on the pressure-sensitive adhesive. The protective film adhesive tape comprises a substrate layer 2 and a pressure-sensitive adhesive layer 1, wherein the pressure-sensitive adhesive layer 1 is coated on the substrate layer 2 in a melt state by the radiation curing adhesive composition provided by the invention and then formed on the substrate 2 through radiation crosslinking.
Description
Technical Field
The invention relates to a radiation-curable adhesive and a pressure-sensitive adhesive and a protective film adhesive tape prepared based on the adhesive.
Background
In the protective film adhesive tape industry, the demand for high-quality protective films is increasing, and various requirements are also increasing. For example, a protective film for protecting a silicon wafer in the semiconductor industry is torn off and observed under a microscope with a certain magnification, and the surface of the silicon wafer cannot have any residual adhesive particles and adhesive marks; the protective film for protecting the flat glass in the flat display industry cannot have any obvious stain on the surface of the glass when observed under a high light lamp, and the influence on the free energy of the surface of the glass is also controlled within a certain range. In addition to the requirement on the performance of residual glue on the surface of an object to be pasted, the easy application performance of the protective film also becomes an important index, and particularly, under the condition that a machine which is not used for applying the protective film by some users can only manually apply the protective film, the poor application performance of the protective film can easily cause bubbles in the product after application, and rework is needed, so that the production efficiency is reduced. The requirement on easy application property narrows the range of selectable adhesives in the formula development of the protective film adhesive tape, and increases the difficulty of the formula development of the protective film adhesive tape industry.
Currently, there are various types of pressure-sensitive adhesives used in protective film tapes, such as polyacrylate type pressure-sensitive adhesives, rubber type (natural rubber and synthetic rubber) pressure-sensitive adhesives, polyurethane type pressure-sensitive adhesives, silicone type pressure-sensitive adhesives, and the like.
The poly (methyl) acrylate pressure-sensitive adhesive is the most widely applied pressure-sensitive adhesive, and because the acrylate (or methyl acrylate) monomers are various, a formula designer can obtain polyacrylate pressure-sensitive adhesives with different viscosities or other special properties by selecting various different monomers for copolymerization, so that a larger selection space is provided. In comparison, the conventional acrylate (or methacrylate) monomers are cheap and have low cost pressure, which is also the reason why many manufacturers prefer the poly (meth) acrylate pressure-sensitive adhesive. The poly (methyl) acrylate pressure-sensitive adhesive applied to the protective film adhesive tape, in particular to the high-grade protective film adhesive tape, has higher requirement on the monomer residue rate in the polymer, the excessive monomer residue has unfriendly smell, the residual adhesive on the adhered object of the protective film is easy to cause, the bonding force between the pressure-sensitive adhesive and the base material is poor, and the monomer migrating to the adhered object can greatly influence the free energy on the solid surface. The protective film prepared by the poly (methyl) acrylate pressure-sensitive adhesive is easy to apply, which is probably related to the movement capability of a poly (methyl) acrylate molecular chain, and the interaction of ester groups and the existence of a large group of a side chain limit the movement capability of the molecular chain. Some formulation engineers may add some small molecular substances (such as esters, silicones, etc.) to the pressure sensitive adhesive formulation to improve the easy application of such protective films, but these small molecular substances are easy to migrate to the surface to contaminate the adherend during the use of the protective film, resulting in poor appearance of the adherend or non-uniform surface free energy.
At present, for the occasions with strict requirements on adhesive residues on the surface of an attached object, the preparation of a protective film by using rubber (natural rubber and synthetic rubber) pressure-sensitive adhesives is not much, mainly because: a rubber pressure-sensitive adhesive is generally added with tackifying resin to improve the viscosity, and the transparency of the rubber pressure-sensitive adhesive is not easy to meet the requirement; secondly, in consideration of processability, a small-molecule softener is added into the rubber pressure-sensitive adhesive formula, and an anti-aging agent is also added to prevent rubber from aging, and the addition of the substances is easy to migrate to the surface to pollute an attached object.
The protective film made of the organic silicon pressure-sensitive adhesive has excellent easy-to-apply performance, which is benefited by the flexibility of an organic silicon macromolecular chain. In addition, due to the inertia of the silicon-oxygen bond, the organic silicon pressure-sensitive adhesive has good temperature resistance, and the prepared protective film is used in many high-temperature resistant occasions. However, due to the non-polarity of the organic silicon molecules and the difficulty in removing some unreacted small molecules in the organic silicon pressure-sensitive adhesive resin, the free energy of the surface of the attached object is greatly reduced, and even the surface of the attached object is changed from hydrophilic to hydrophobic. In addition, the organic silicon pressure-sensitive adhesive usually needs benzene solvents to be dissolved, which is not beneficial to environmental protection, and thus the use of the pressure-sensitive adhesive is limited.
The application of polyurethane pressure-sensitive adhesive to the protective film industry is also starting, wherein the protective film made of polyether polyurethane pressure-sensitive adhesive has excellent easy-to-apply property and is equivalent to the protective film made of organic silicon pressure-sensitive adhesive. The polyether polyurethane pressure-sensitive adhesive is prepared by reacting polyether macromolecules and polyisocyanate, the polyether macromolecules are polar macromolecules, and residual micromolecules are easy to remove during production of the polyether macromolecules, so that the polyether polyurethane pressure-sensitive adhesive is not easy to pollute the surface of a pasted object and has little influence on the surface free energy. The polyurethane pressure-sensitive adhesive is suitable for occasions where poly (methyl) acrylate pressure-sensitive adhesives and silicone pressure-sensitive adhesives are not suitable, but the polyurethane pressure-sensitive adhesive has poor temperature resistance and is easy to decompose at higher temperature to cause adhesive residue, so the polyurethane pressure-sensitive adhesive is not suitable for occasions where high-temperature process technology exists.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a radiation-curable adhesive composition and a pressure-sensitive adhesive formed based on the adhesive composition, wherein the pressure-sensitive adhesive prepared from the adhesive composition has excellent wettability on a solid surface and excellent adhesive residue prevention performance; the invention also provides a protective film adhesive tape based on the pressure-sensitive adhesive, and the manufacturing process of the protective film adhesive tape is environment-friendly, easy to attach to an attached object and not easy to cause adhesive residue on the surface of the attached object.
In order to achieve the above object, the present invention provides a radiation curable adhesive composition comprising a radiation curable oligomer, and a radiation curable reactive diluent; the molecular chain of the oligomer has a polypropylene oxide structure shown in a formula (1):
wherein the degree of polymerization n > 5.
Further, the oligomer is present in a concentration of 25 to 99 wt%, based on the total mass of the radiation curable adhesive composition.
Further, the mass percentage of the polypropylene oxide structure in the radiation curing adhesive composition is 20-95 wt%.
Further, the adhesive composition also comprises a photoinitiator, and the mass percentage of the photoinitiator in the radiation curing adhesive composition is 0.01-5 wt%.
Further, the molecular chain of the oligomer has an acryloyloxy group or a methacryloyloxy group as a radiation-curable group.
Furthermore, the molecular chain of the oligomer can be linear or branched, and the number average molecular weight is 500-50000.
Further, the radiation-curable reactive diluent has at least one reactive group capable of participating in a radiation-curing reaction.
In order to achieve the above object, the present invention provides a pressure-sensitive adhesive, which is obtained by radiation crosslinking of the radiation curable adhesive composition.
In order to achieve the purpose, the protective film adhesive tape provided by the invention comprises a substrate layer 2 and a pressure-sensitive adhesive layer 1; the pressure-sensitive adhesive layer 1 is coated on the base material layer 2 in a melt state by the radiation curing adhesive composition, and then is formed on the base material layer 2 through radiation crosslinking.
Further, the gluing amount of the radiation curing adhesive composition on the base material of the protective film adhesive tape is 5-100g/m2。
Further, the base material of the protective film adhesive tape is a PET film, a TPU film, a polyolefin film or a PVC film.
The invention provides a radiation-curable adhesive composition, and the pressure-sensitive adhesive prepared from the adhesive composition has excellent performance of preventing adhesive residue, small influence on the surface free energy of an attached object, and good wettability of a prepared protective film on the surface of the attached object, and is easy to apply.
The invention provides a radiation-curable adhesive composition, which belongs to a solvent-free adhesive, and has no solvent emission and environmental pollution in the process of preparing a protective film adhesive tape.
The protective film adhesive tape provided by the invention is cured by radiation, so that the heating for volatilizing a solvent and crosslinking and curing an adhesive are not needed as in the preparation of a common protective film adhesive tape, and the energy consumption in the production process of the protective film adhesive tape is greatly reduced.
The protective film adhesive tape provided by the invention is used for occasions with high requirements on surface appearance and easy application in construction.
Drawings
Fig. 1 is a schematic cross-sectional view of a protective tape according to an embodiment of the present invention.
Reference numbers in the figures: a substrate layer-2; pressure-sensitive adhesive layer-1.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
The radiation-cured adhesive composition comprises a molecular chain with a polypropylene oxide structure, a radiation-curable oligomer and a radiation-curable reactive diluent.
The polyoxypropylene structure herein is preferably as follows:
wherein the degree of polymerization n > 5.
The oligomers can be classified herein as polyether urethane acrylate oligomers, polyether acrylate oligomers, and derivatives of these two types of light-curable oligomers.
The preparation of the oligomers is described in detail below:
preparation of polyether structure in oligomer molecular chain
The polyether acrylate oligomer is obtained by esterifying polyether polyol and acrylic acid. The polyether polyol in the present invention has a polyoxypropylene structure in its molecular chain, but is not limited to a polyoxypropylene structure, and also a polyoxyethylene or other polyol structure. The polyether polyol is synthesized by copolymerizing an initiator and an oxyalkylene monomer. Compounds containing two active hydrogen atoms are useful as initiators for the synthesis of polyether polyols. The initiator of the polyether glycol can be ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, neopentyl glycol, bisphenol A, water and the like. Wherein 1, 2-propylene glycol and ethylene glycol are used as more initiators in the actual production of polyether glycol. The initiator for synthesizing polyether triol is glycerine, trimethylol propane, ethanolamine, diethanolamine and triethanolamine, and glycerine and trimethylol propane are used in practical production. Ethylenediamine, toluenediamine, methylenedianiline, pentaerythritol, etc. can be used as an initiator for synthesizing polyether tetrol. As the initiator for synthesizing other polyether polyols with higher functionality, polyhydroxyl compounds such as xylitol, sorbitol and sucrose can be used. The polyether polyol with high functionality is a nonlinear molecular chain, has high viscosity, is not beneficial to production and processing, and a mixed polyol initiator with high functionality and low functionality, such as sorbitol-glycerol, sorbitol-propylene glycol and the like, is often adopted in actual production.
The monomers for preparing the polyether polyol in the present invention are oxyalkylene monomers such as propylene oxide, ethylene oxide, or a mixture of propylene oxide and ethylene oxide, etc. Among them, propylene oxide is an indispensable monomer. The oxyalkylene monomer is subjected to ring-opening polymerization to form polyether polyol with a certain molecular weight and a molecular chain structure. The ring-opening polymerization of alkylene oxide monomers requires, in addition to the initiator, a certain catalyst, usually potassium hydroxide, which some manufacturers have also used double metal cyanide complexes to obtain polyether polyols of low unsaturation.
The usual preparation of polyether polyols is as follows: adding an initiator and a catalyst into a catalyst preparation kettle, heating to 80-100 ℃, and vacuumizing to remove water in the catalyst to generate potassium alkoxide. And adding the prepared catalyst mixture into a polymerization reaction kettle, heating to 90-120 ℃, introducing a polyoxyalkylene monomer, and keeping the pressure in the kettle between 0.07-0.35 MPa. Keeping the temperature and the pressure unchanged, continuously introducing the oxyalkylene monomer until the designed molecular weight is reached, stopping the reaction, distilling out the residual oxyalkylene monomer, transferring the generated polyether polyol mixture into a neutralization kettle, neutralizing with an acidic substance, filtering, refining and adding a stabilizer to obtain the finished product polyether polyol.
The polyether polyols to which the present invention relates include not only polyoxypropylene homopolymers but also random and block copolymers of propylene oxide and ethylene oxide. The random copolymer is prepared by introducing a mixture of propylene oxide and ethylene oxide in a certain proportion into a polymerization reaction kettle in the production process. The block copolymer is produced through the reaction of first introducing propylene oxide and then introducing metered ethylene oxide for further reaction after the reaction of propylene oxide polyether to form polyethylene oxide block. The polyether polyols to which the present invention relates may be copolymers of tetrahydrofuran and propylene oxide in addition to copolymers of propylene oxide and ethylene oxide. The tetrahydrofuran and propylene oxide glycol can improve the cohesive strength, hydrolysis resistance, wear resistance, mildew resistance, low temperature resistance and other properties of the adhesive. The preparation of tetrahydrofuran and propylene oxide glycol is different from the preparation process of the above-mentioned polyoxypropylene and ethylene oxide copolyether, and the copolymer is prepared by using cation to initiate ring-opening polymerization at low temperature, then making neutralization, water washing, filtering and decolouring treatment. The polymerization process adopts catalysts such as fluorosulfonic acid catalysis, acetic acid-perchloric acid catalysis and the like.
Preparation of (di) oligomers
In the method for preparing the polyether structure in the molecular chain of the oligomer, in order to enable the polyether polyol to be crosslinked in a radiation curing mode, a functional group capable of being polymerized by radiation is introduced into the molecular chain, the invention introduces acryloxy or methacryloxy as a group capable of being cured by radiation, and the obtained oligomer can be called polyether acrylate or polyether urethane acrylate.
The polyether acrylate is obtained by esterifying polyether polyol with (meth) acrylic acid. Since the esterification reaction is generally carried out under acidic conditions, but ether bonds in the polyether molecular chain are easily broken under acidic conditions, the polyether acrylate is generally prepared by a transesterification reaction. Polyether glycol, excessive (methyl) acrylate, polymerization inhibitor and catalyst are mixed, heated to a certain temperature to carry out ester exchange reaction, the generated micromolecular alcohol and (methyl) acrylate form an azeotrope to be distilled out, the azeotrope passes through a fractionating tower, the (methyl) acrylate returns to a reaction kettle from beginning to end, the micromolecular alcohol is fractionated out, the ester exchange reaction is fully completed, and unreacted (methyl) acrylate is removed by reduced pressure distillation to obtain the polyether acrylate.
Polyether urethane acrylates are obtained by reacting polyether polyols with hydroxy (meth) acrylates by means of diisocyanates. The isocyanate groups in the diisocyanate react with the hydroxyl groups in the polyether polyol and the hydroxyl groups in the hydroxy (meth) acrylate, respectively, to form urethane bonds linking the (meth) acryloyloxy groups to the polyether polyol molecular chains.
Diisocyanates used for the synthesis of polyether urethane acrylate are generally classified into aromatic diisocyanates and aliphatic diisocyanates, mainly toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like.
Examples of the hydroxy (meth) acrylate used for the synthesis of the polyether urethane acrylate include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, and the like. Of these, trimethylolpropane diacrylate and pentaerythritol triacrylate are generally used to prepare a multifunctional polyether urethane acrylate oligomer.
In the process of preparing polyether urethane acrylate, in order to promote the reaction between hydroxyl groups in polyether polyol and (meth) acrylate and isocyanate groups in diisocyanate, a small amount of catalyst is usually added, and general catalysts include tertiary amines, organic metal compounds and the like, such as triethanolamine, triethylenediamine, dibutyltin laurate, stannous octoate, cobalt octoate, lead octoate, zinc naphthenate and the like. The tertiary amine catalyst has obvious catalytic action on aromatic diisocyanate, but has weak catalytic action on aliphatic; the organometallic compound has a strong catalytic action on both aromatic diisocyanates and aliphatic diisocyanates. Organometallic compounds such as dibutyltin dilaurate are therefore the more catalysts used in the process for preparing polyether urethane acrylates.
The synthesis of polyether urethane acrylate is completed through two-step reaction, namely, diisocyanate reacts with hydroxyl in polyether polyol and hydroxyl in (methyl) acrylic acid hydroxy ester respectively. There are generally two synthetic routes: reacting diisocyanate with polyether polyol and then (methyl) acrylic acid hydroxyl ester; the diisocyanate is reacted first with the hydroxy (meth) acrylate and then with the polyether polyol. In the first synthesis route, the retention time of the (methyl) acrylic acid hydroxyl ester in the reaction kettle is short, which is beneficial to the (methyl) acrylic acid hydroxyl ester to generate gel due to polymerization caused by too long heating time, but the reaction of the (methyl) acrylic acid hydroxyl ester and diisocyanate is possibly incomplete, and a small amount of unreacted (methyl) acrylic acid hydroxyl ester monomer exists. In the second synthesis route, the hydroxy (meth) acrylate is heated for a longer time, so that the possibility of polymerization is increased, and more polymerization inhibitor is required to be added. Therefore, the synthesis process needs to be selected reasonably according to different reactivity of diisocyanate with hydroxyl in polyether polyol and (methyl) acrylic acid hydroxy ester.
The reaction of isocyanates with hydroxyl groups is exothermic and too rapid an exotherm cannot be ruled out during the reaction, which leads to a temperature increase which leads to gelling of the reaction mass. In general, a dropping process is adopted in the preparation process, that is, polyether polyol or hydroxy (meth) acrylate is slowly dropped into diisocyanate mixed with a catalyst, so as to avoid the temperature from being sharply increased due to heat accumulation.
The adhesive composition of the present invention further comprises a radiation curable reactive diluent. The reactive diluent has one or more reactive groups that can participate in the radiation curing reaction. The reactive diluent may be classified into a monofunctional reactive diluent and a polyfunctional reactive diluent. Typical monofunctional reactive diluents are butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, ethoxyethoxyethyl acrylate, glycidyl methacrylate, isobornyl (meth) acrylate, tetrahydrofuryl methyl acrylate, phenoxyethyl acrylate, vinyl acetate, N-vinylpyrrolidone, 4-tert-butylcyclohexyl acrylate, ethyleneureethoxy methacrylate, m-phenoxybenzyl acrylate, dicyclopentenyl ethoxylated acrylate, 2- [ [ (butylamino) carbonyl ] oxo ] ethyl acrylate, 2-phenoxyethyl acrylate, ethoxylated phenoxyacrylate, 3, 5-trimethylcyclohexyl acrylate, ethoxylated phenoxyethyl acrylate, 2-phenoxyethyl acrylate, ethoxylated phenoxyethyl acrylate, 3, 5-trimethylcyclohexyl acrylate, ethoxylated phenoxyethyl acrylate, O-phenylphenoxyethyl acrylate, 2- (p-cumyl-phenoxy) -ethyl acrylate, ethoxyethoxyethyl acrylate, cyclotrimethylolpropane formal acrylate, tetrahydrofurfuryl acrylate, 2- (1, 2-cyclohexanedicarboximide) ethyl acrylate, 2- (4-cyclohexene-1, 2-dicarboximide) ethyl acrylate, stearic acid acrylate, propoxylated nonylphenol acrylate, octadecato docosyl acrylate, dicyclopentenylethoxylated methacrylate, isodecyl methacrylate, 2-phenoxyethyl methacrylate, isotridecyl methacrylate, tetrahydrofurfuryl methacrylate, lauric acid methacrylate, stearic acid methacrylate, tetrahydrofurfuryl acrylate, laurylic acid methacrylate, laurylic acid, Cyclohexyl methacrylate, benzyl (meth) acrylate, dicyclopentanyl methacrylate, 2-ethylhexyl methacrylate, and the like.
The bifunctional diluent is selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 4-butanediol diacrylate, 1, 3-butanediol diacrylate, 1, 6-hexanediol diacrylate, ethoxylated 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, phthalic acid ethylene glycol diacrylate, 3-hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropyl diacrylate, tricyclodecane dimethanol diacrylate, dioxane diol diacrylate, ethoxylated bisphenol A di (meth) acrylate, (ethoxylated) 2-methyl-1, 3-propanediol diacrylate, ethylene glycol diacrylate, propylene glycol, 3-methyl-1, 5-pentanediol diacrylate, tricyclodecane dimethanol dimethacrylate, 2-hydroxyethyl methacrylate phosphate, and the like.
Higher functional diluents are tris (2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, propoxylated glycerol tri (meth) acrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like.
The reactive diluent in the adhesive composition of the invention can be one or a mixture of more of the above monofunctional monomers and polyfunctional monomers.
In the adhesive composition, in order to realize radiation curing, a photoinitiator is required to be added, the photoinitiator absorbs radiation energy to generate free radicals to initiate unsaturated bonds to generate polymerization reaction, the photoinitiator can be divided into a cracking type photoinitiator and a hydrogen abstraction type photoinitiator according to different action mechanisms of generating free radicals, the hydrogen abstraction type photoinitiator needs a hydrogen donor to generate active free radicals, and the hydrogen donor can be provided by an auxiliary initiator or a polymer macromolecule, wherein the cracking type photoinitiator comprises benzoin and derivatives thereof, α' -dimethyl benzil ketal, α -diethoxy acetophenone, 2-hydroxy-2-methyl-phenyl acetone, 1-hydroxy-cyclohexyl benzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone-1, 2-methyl 1- (4-methyl mercapto phenyl) -2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2,4, 6-trimethyl benzoyl-ethoxy-phenyl phosphine oxide, 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide and the like, the hydrogen abstraction type photoinitiator, 2,4, 6-trimethyl phenyl benzophenone, 4-trimethyl phenyl-isopropyl benzophenone, 5-tertiary amine, 5-dimethyl-phenyl-3-methyl-phenyl-benzophenone, 4-ethyl-3, 5-dimethyl-3-phenyl-3-methyl-phenyl-benzophenone, and the like.
In addition to the above components, the adhesive composition of the present invention may contain any suitable other components, including an ultraviolet absorber, a leveling agent, an anti-aging agent, an antioxidant, an antistatic agent, etc., without affecting the effects of the present invention.
The radiation curable adhesive composition thus constituted is preferably embodied in a concentration of oligomer of 25 to 99 wt%. Furthermore, the mass percentage of the polyoxypropylene structure in the oligomer in the radiation-curable adhesive composition is 20-95 wt%.
The molecular chain of the oligomer may be linear or branched, and the number average molecular weight is 500 to 50000.
Such radiation curable adhesive compositions can be directly crosslinked by radiation to give the corresponding pressure sensitive adhesives.
Accordingly, a corresponding protective film tape can also be formed. As shown in fig. 1, it is a protective film tape formed based on the above radiation curable adhesive composition.
As can be seen from the figure, the protective film tape mainly includes a base material layer 2 and a pressure-sensitive adhesive layer 1.
The substrate layer 2 may be formed of a PET film, a TPU film, a polyolefin film, a PVC film, or the like.
The pressure-sensitive adhesive layer 1 is coated on the substrate layer 2 in a melt state from the radiation-curable adhesive composition given in this example, and then directly molded on the substrate layer 2 by radiation crosslinking.
Specifically, the radiation curing adhesive composition prepared based on the scheme is used at room temperature or higher temperature<60 ℃) in the melt state onto the substrate layer 2, the sizing amount here preferably being from 5 to 100g/m2And subsequently exposed to radiation of a certain energy to crosslink the composition.
The adhesive composition formed by the method belongs to a solvent-free adhesive, and the pressure-sensitive adhesive prepared by the adhesive has excellent performance of preventing adhesive residue and small influence on the surface free energy of an object to be adhered, and can be used for occasions with high requirement on the surface appearance, excellent performance of preventing adhesive residue and easy application in construction;
the protective film adhesive tape prepared from the pressure-sensitive adhesive is cured by radiation, so that the solvent is not required to be volatilized and the adhesive is not required to be crosslinked and cured like the preparation of a common protective film adhesive tape, the energy consumption in the production process of the protective film adhesive tape is greatly reduced, no solvent is discharged in the preparation process, the environment is polluted, the wettability on the surface of an attached object is good, and the adhesive is easy to apply.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer. Unless otherwise indicated, all parts are parts by weight, all percentages are percentages by weight, and the polymer molecular weight is the number average molecular weight.
Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
[ example 1]
Mixing polyether diol GE-220A and methyl methacrylate in a molar ratio of 1:6, adding a proper amount of p-methoxyphenol and a catalyst, heating to react until boiling, reacting to generate methanol and methyl methacrylate to form a copolymer, rectifying to remove the methanol, stopping the reaction when the temperature of a rectification column head is reduced to room temperature, cooling, precipitating, separating to remove the catalyst, and distilling under reduced pressure to remove residual methyl methacrylate and methanol to obtain polyether acrylate 1.
The adhesive composition was formulated as follows:
1:80 parts of polyether acrylate;
ethoxy ethyl acrylate: 15 parts of (1);
trimethylolpropane triacrylate: 5 parts of a mixture;
2-hydroxy-2-methyl-phenylacetone-1: 0.5 part;
dissolving the above components, mixing, and coating on PET with wire rod with the coating amount of 20g/m2Then irradiating and curing under an ultraviolet mercury lamp with the radiation energy of 500mJ/cm2And obtaining the protective adhesive tape. The test items and results are shown in table one.
[ example 2]
0.5mol of polyether diol GE-220A, 1mol of toluene diisocyanate, 0.1% of dibutyltin dilaurate and 0.05% of p-methoxyphenol are mixed and added into a reaction kettle, the reaction is carried out at 60 ℃ until the-NCO value reaches a calculated value, 1mol of hydroxyethyl acrylate is added, the temperature is raised to 70 ℃, and the reaction is carried out until the-NCO value approaches 0, so that the polyether urethane acrylate 1 is obtained.
The adhesive composition was formulated as follows:
1:80 parts of polyether urethane acrylate;
ethoxy ethyl acrylate: 15 parts of (1);
trimethylolpropane triacrylate: 5 parts of a mixture;
3-hydroxy-2-methyl-phenylacetone-1: 0.5 part;
dissolving the above components, mixing, and coating on PET with wire rod with the coating amount of 20g/m2Then irradiating and curing under an ultraviolet mercury lamp with the radiation energy of 500mJ/cm2And obtaining the protective adhesive tape. The test items and results are shown in table one.
[ example 3]
Mixing 0.5mol of polyether glycol GE-220A, 0.1% of dibutyltin dilaurate and 1mol of hexamethylene diisocyanate, adding into a reaction kettle, reacting at 70-75 ℃ for 3-4 hours, cooling to 60 ℃, adding 1mol of hydroxyethyl acrylate and 0.1% of hydroquinone, and reacting at 60-65 ℃ until the-NCO value is close to 0 to obtain the polyether polyurethane acrylate 2.
The adhesive composition was formulated as follows:
polyether urethane acrylate 2:80 parts
Ethoxy ethyl acrylate: 15 portions of
Trimethylolpropane triacrylate: 5 portions of
4-hydroxy-2-methyl-phenylacetone-1: 0.5 portion
Dissolving the above components, mixing, and coating on PET with wire rod with the coating amount of 20g/m2Then irradiating and curing under an ultraviolet mercury lamp with the radiation energy of 500mJ/cm2And obtaining the protective adhesive tape. The test items and results are shown in table one.
[ example 4]
Adding 0.31mol of hexamethylene diisocyanate, 0.1% of dibutyltin dilaurate and 0.1% of hydroquinone into a reaction kettle, stirring uniformly, introducing N2 for protection, slowly dropwise adding 0.3mol of hydroxyethyl acrylate, controlling the temperature to be 40-50 ℃, reacting until the-NCO value reaches a calculated value, adding 0.1mol of polyether triol GEP-560S, slowly heating to 75 ℃, reacting for 3-4 hours, and stopping the reaction until the-NCO value content is less than 0.2%, thereby obtaining the polyether urethane acrylate 3.
The adhesive composition was formulated as follows:
85 parts of polyether urethane acrylate;
ethoxy ethyl acrylate: 10 parts of (A);
trimethylolpropane triacrylate: 5 parts of a mixture;
5-hydroxy-2-methyl-phenylacetone-1: 0.5 part;
dissolving the above components, mixing, and coating on PET with wire rod with the coating amount of 20g/m2Then irradiating and curing under an ultraviolet mercury lamp with the radiation energy of 500mJ/cm2And obtaining the protective adhesive tape. The test items and results are shown in table one.
[ example 5]
The adhesive composition was formulated as follows:
1:45 parts of polyether urethane acrylate;
polyether urethane acrylate 3: 45 parts of (1);
ethoxy ethyl acrylate: 8 parts of a mixture;
trimethylolpropane triacrylate: 2 parts of (1);
6-hydroxy-2-methyl-phenylacetone-1: 0.5 part;
dissolving the above components, mixing, and coating on PET with wire rod with the coating amount of 20g/m2Then irradiating and curing under an ultraviolet mercury lamp with the radiation energy of 500mJ/cm2And obtaining the protective adhesive tape. The test items and results are shown in table one.
| |
|
Ease of application test ③ | |
| Example one | No adhesive residue | No residual print, water drop angle of 40-50 ° | Superior food |
| Example two | No adhesive residue | No residual print, water drop angle of 40-50 ° | Superior food |
| EXAMPLE III | No adhesive residue | No residual print, water drop angle of 40-50 ° | Superior food |
| Example four | No adhesive residue | No residual print, water drop angle of 40-50 ° | Superior food |
| EXAMPLE five | No adhesive residue | No residual print, water drop angle of 40-50 ° | Superior food |
| Acrylic adhesive protective film | No adhesive residue | No residual print, water drop angle of 80-90 ° | With air bubbles, it cannot be completely self-leveling |
| Polyurethane glue protective film | Severe adhesive residue | No residual print, water drop angle of 40-50 ° | Superior food |
The test patterns referred to in the table above are illustrated as follows:
(1) the initial water drop angle of the surface of the mother glass is 20-30 degrees.
(2) The temperature resistance test method comprises the steps of pasting the protective film adhesive tape on the plain glass, baking at 150 ℃ for 3 hours, and observing the residual adhesive on the surface of the glass.
(3) The pollution test method comprises the following steps: the sample was attached to a mother glass, treated at 60 ℃ and 90% RH for 168 hours, and then the surface condition of the mother glass was observed by removing the protective tape, and the angle of water drop on the surface was changed.
(4) Testing the easy application property: cutting the protective film into a shape of 50mm wide × 100mm long, contacting one end of the width side with the mother glass, lifting the other end, placing the protective film to allow the protective film to self-level, observing whether the protective film can self-level within a specified time, and flatly applying the protective film on the mother glass.
As shown in the table I, the surface protective tape prepared by the embodiment of the present invention has excellent adhesive residue prevention performance, easy application performance and high temperature resistance.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A radiation curable adhesive composition comprising a radiation curable oligomer, and a radiation curable reactive diluent; the molecular chain of the oligomer has a polypropylene oxide structure shown in a formula (1):
wherein the degree of polymerization n > 5.
2. The radiation curable adhesive composition of claim 1, wherein said oligomer is present in a concentration of 25 to 99 wt.%, based on the total mass of said radiation curable adhesive composition.
3. The radiation curable adhesive composition according to claim 1 or 2, wherein the polyoxypropylene structure is present in the radiation curable adhesive composition in an amount of 20-95 wt%.
4. The radiation curable adhesive composition according to claim 1, further comprising a photoinitiator, wherein the photoinitiator is present in the radiation curable adhesive composition in an amount of 0.01 to 5 wt%.
5. The radiation curable adhesive composition according to claim 1, wherein said oligomer has acryloxy or methacryloxy groups as radiation curable groups on its molecular chain.
6. The radiation curable adhesive composition of claim 1, wherein the molecular chain of the oligomer is linear or branched and has a number average molecular weight of 500-50000.
7. The radiation curable adhesive composition of claim 1, wherein said radiation curable reactive diluent has at least one reactive group capable of participating in a radiation cure reaction.
8. A pressure-sensitive adhesive obtained by radiation crosslinking the radiation curable adhesive composition according to any one of claims 1 to 7.
9. A protective film adhesive tape comprises a substrate layer 2 and a pressure-sensitive adhesive layer 1, wherein the pressure-sensitive adhesive layer 1 is formed by coating the radiation-curable adhesive composition of any one of claims 1 to 7 on the substrate layer 2 in a melt state and then performing radiation crosslinking on the substrate layer 2.
10. Protective film tape according to claim 9, wherein the radiation curable adhesive composition is applied to the substrate in an amount of 5-100g/m2。
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